CN102558460B - Acrylate grafted aqueous polyurethane emulsion and preparation method thereof - Google Patents
Acrylate grafted aqueous polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN102558460B CN102558460B CN 201110458710 CN201110458710A CN102558460B CN 102558460 B CN102558460 B CN 102558460B CN 201110458710 CN201110458710 CN 201110458710 CN 201110458710 A CN201110458710 A CN 201110458710A CN 102558460 B CN102558460 B CN 102558460B
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Abstract
The invention discloses acrylate grafted aqueous polyurethane emulsion and a preparation method thereof. The emulsion is characterized is prepared from polyether polyol, dimethylol propionic acid, isophorone diisocyanate, ethylenediamine, hydroxyethyl acrylate and the like. The preparation method comprises the following steps: carrying out prepolymerization on polyether polyol, dimethylol propionic acid and isophorone diisocyanate so as to introduce a hydrophilic monomer; adding ethylenediamine and hydroxyethyl acrylate to carry out chain extension so as to introduce a functional monomer; adding an acrylate mixed monomer so as to reduce system viscosity; adding triethylamine for neutralization; adding deionized water for emulsification and dispersion under the condition of high-speed shearing to obtain emulsion; then dropwise adding the acrylate mixed monomer and an initiator, raising the temperature and carrying out reaction; and cooling to obtain the PUA (polyurethane-acrylate) emulsion. The emulsion prepared by the method has small grain size and excellent performances such as mechanical performance, is narrowly distributed and can be widely applied to industry fields such as leather finish, coatings, adhesives and fabric coatings.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of acrylic ester grafted aqueous polyurethane emulsion and preparation method thereof.
Background technology
In recent years, along with the environmental regulation increasingly stringent, the petroleum products cost constantly raise, and people are more and more paid close attention to as the aqueous polyurethane of dispersion medium substituting organic solvent with water.Characteristics such as aqueous polyurethane emulsion has safety, easily stores, easy to use, and cost is low, the a lot of excellent performances of solvent borne polyurethane have been inherited simultaneously, it is strong etc. that, wear resistance adjustable, low temperature resistant as soft durometer reaches adhesive power well, but exist that film forming speed is slow, poor to the non-polar substrate wettability, tack is low, poor water resistance, thermotolerance are not ideal enough etc.The acrylate series products has advantages such as physical strength height, ageing-resistant, wear resistance, solvent resistance and water-tolerant, but has the shortcoming of hot sticky cold crisp.Acrylate and aqueous polyurethane is compound, can overcome shortcoming separately, make both advantage obtain complementation, accomplish to maximize favourable factors and minimize unfavourable ones, film performance is significantly improved, and the composite emulsion of preparation (PUA) is widely used in industrial circles such as leather finish, coating, tackiness agent, fabric coating.
Summary of the invention
The objective of the invention is based on the deficiencies in the prior art, a kind of acrylic ester grafted aqueous polyurethane emulsion and preparation method thereof is provided.
In order to achieve the above object, the invention provides a kind of acrylic ester grafted aqueous polyurethane emulsion, it is characterized in that, comprise following component by the weight part meter:
100 parts of polyether glycols;
Dimethylol propionic acid 5-10 part;
Isophorone diisocyanate 30-35 part;
Triethylamine 3-5 part;
Quadrol 2-3 part;
Hydroxyethyl acrylate 5-40 part;
Acrylate mixing monomer 100-200 part;
Initiator 10-20 part;
Deionized water 350-400 part.
Preferably, described polyether glycol is polyether glycol N220.
Preferably, described acrylate mixing monomer is the mixture of soft monomer butyl acrylate and hard monomer methyl methacrylate, and the mass ratio of soft monomer butyl acrylate and hard monomer methyl methacrylate is 1.5-2:1.
Preferably, described initiator is Diisopropyl azodicarboxylate.
The present invention also provides the preparation method of the aqueous polyurethane emulsion of aforesaid propylene acid esters grafting, it is characterized in that, may further comprise the steps:
The first step: with the vacuum hydro-extraction under 90-100 ℃ of condition in proportion of polyether glycol, dimethylol propionic acid, put into reactor, be warming up to 80-85 ℃;
Second step: add isophorone diisocyanate in the reactor in the first step, carry out prepolymerization reaction, reacted 3 hours;
The 3rd step: add quadrol and Hydroxyethyl acrylate in the reactor in second step, carry out chain extending reaction, reacted 1 hour, be cooled to 50 ℃;
The 4th step: add acrylate mixing monomer 30-50 part in the reactor in the 3rd step, be cooled to 30-35 ℃;
The 5th step: add triethylamine in the reactor in the 4th step, stir 8-10min, under the 800-1000r/min high speed shear, add deionized water emulsification, disperse 25-30min, obtain emulsion;
The 6th step: go on foot even remaining acrylate mixing monomer and the initiator of dripping in the emulsion that obtains the 5th, in 2-3h, dropwise, be warming up to 80-85 ℃ of reaction 1-2h, be cooled to room temperature, obtain the PUA emulsion.
Beneficial effect of the present invention:
(1) in the process of preparation polyurethane dispersing liquid, introduce hydrophilic dimethylol propionic acid, do not need to add emulsifying agent, owing to contain hydrophilic composition in the polyurethane molecular, so need not powerful the stirring and self disperse to form emulsion and good stability at emulsifying stage.
(2) initiator of the inventive method employing is Diisopropyl azodicarboxylate, and dispersion effect is good, and the emulsion particle diameter of preparation is little, be evenly distributed, and excellent propertys such as various mechanics, range of application is more extensive.
(3) the product environment protection health of the present invention's preparation, no toxic gas volatilization in the use.
Embodiment
Describe the present invention below in conjunction with embodiment.
Polyether glycol is selected polyether glycol N220 for use among the embodiment 1-3; Acrylate mixing monomer is the mixture of soft monomer butyl acrylate and hard monomer methyl methacrylate, and the mass ratio of soft monomer butyl acrylate and hard monomer methyl methacrylate is 1.5-2:1; Initiator is selected Diisopropyl azodicarboxylate for use.
Embodiment 1
With 100 parts of polyether glycols, 5.5 parts of vacuum hydro-extractions under 95 ℃ of conditions of dimethylol propionic acid, put into dry, have in the four-hole boiling flask of thermometer, be warming up to 85 ℃, adding 30 parts of isophorone diisocyanates carries out prepolymerization reaction and introduces hydrophilic monomer, react after 3 hours, add 2 parts of quadrols and 5 parts of Hydroxyethyl acrylates, carry out chain extending reaction and introduce functional monomer, react and be cooled to 50 ℃ in 1 hour, add 20 parts of butyl acrylates and methyl methacrylate and reduce system viscosity for 10 parts, add 3 parts of triethylamine neutralizations after continuing to be cooled to 30 ℃ again, stir 8min, the deionized water emulsification that adds 350 parts under the 800r/min high speed shear disperses 25min, obtains emulsion, continue 50 parts of 100 parts of dropwise addition of acrylic acid butyl esters and methyl methacrylates, 10 parts of Diisopropyl azodicarboxylates, evenly dropwise in 3h, be warming up to 80 ℃ of reaction 2h, cooling obtains the PUA emulsion.
Embodiment 2
With 100 parts of polyether glycols, 7 parts of vacuum hydro-extractions under 90 ℃ of conditions of dimethylol propionic acid, put into dry, have in the four-hole boiling flask of thermometer, be warming up to 85 ℃, adding 32 parts of isophorone diisocyanates carries out prepolymerization reaction and introduces hydrophilic monomer, react after 3 hours, add 2.5 parts of quadrols and 15 parts of Hydroxyethyl acrylates, carry out chain extending reaction and introduce functional monomer, react and be cooled to 50 ℃ in 1 hour, add 21 parts of butyl acrylates and methyl methacrylate and reduce system viscosity for 13 parts, add 4 parts of triethylamine neutralizations after continuing to be cooled to 32 ℃ again, stir 9min, the deionized water emulsification that adds 380 parts under the 900r/min high speed shear disperses 28min, obtains emulsion, continue 50 parts of 80 parts of dropwise addition of acrylic acid butyl esters and methyl methacrylates, 15 parts of Diisopropyl azodicarboxylates, evenly dropwise in 3h, be warming up to 80 ℃ of reaction 2h, cooling obtains the PUA emulsion.
Embodiment 3
With 100 parts of polyether glycols, 10 parts of vacuum hydro-extractions under 100 ℃ of conditions of dimethylol propionic acid, put into dry, have in the four-hole boiling flask of thermometer, be warming up to 85 ℃, adding 35 parts of isophorone diisocyanates carries out prepolymerization reaction and introduces hydrophilic monomer, react after 3 hours, add 3 parts of quadrols and 40 parts of Hydroxyethyl acrylates, carry out chain extending reaction and introduce functional monomer, react and be cooled to 50 ℃ in 1 hour, add 25 parts of butyl acrylates and methyl methacrylate and reduce system viscosity for 15 parts, add 5 parts of triethylamine neutralizations after continuing to be cooled to 35 ℃ again, stir 9min, the deionized water emulsification that adds 400 parts under the 1000r/min high speed shear disperses 25min, obtains emulsion, continue 60 parts of 98 parts of dropwise addition of acrylic acid butyl esters and methyl methacrylates, 20 parts of Diisopropyl azodicarboxylates, evenly dropwise in 3h, be warming up to 80 ℃ of reaction 2h, cooling obtains the PUA emulsion.
The PUA emulsion that embodiment 1-3 makes is tested its viscosity by GB/T2974-1995, test its stripping strength by GB/T2790-1995, press GB/T2974-1995 test monomer whose transformation efficiency, test result is as follows:
| Embodiment | Viscosity/s | Stripping strength/(N/15mm) | Monomer conversion/% | Emulsion appearance |
| 1 | 26.03 | 1.68 | 94.9 | Oyster white, uniform and stable |
| 2 | 25.86 | 1.65 | 95.3 | Oyster white, uniform and stable |
| 3 | 25.88 | 1.72 | 95.7 | Oyster white, uniform and stable |
As seen from the above table, the acrylic ester grafted aqueous polyurethane emulsion of the present invention's preparation is uniform and stable, every excellent performance, monomer conversion height in the preparation process simultaneously.
Claims (4)
1. the preparation method of an acrylic ester grafted aqueous polyurethane emulsion is characterized in that, described acrylic ester grafted aqueous polyurethane emulsion comprises following component by the weight part meter:
100 parts of polyether glycols;
Dimethylol propionic acid 5-10 part;
Isophorone diisocyanate 30-35 part;
Triethylamine 3-5 part;
Quadrol 2-3 part;
Hydroxyethyl acrylate 5-40 part;
Acrylate mixing monomer 100-200 part;
Initiator 10-20 part;
Deionized water 350-400 part;
The preparation method may further comprise the steps:
The first step: with the vacuum hydro-extraction under 90-100 ℃ of condition in proportion of polyether glycol, dimethylol propionic acid, put into reactor, be warming up to 80-85 ℃;
Second step: add isophorone diisocyanate in the reactor in the first step, carry out prepolymerization reaction, reacted 3 hours;
The 3rd step: add quadrol and Hydroxyethyl acrylate in the reactor in second step, carry out chain extending reaction, reacted 1 hour, be cooled to 50 ℃;
The 4th step: add acrylate mixing monomer 30-50 part in the reactor in the 3rd step, be cooled to 30-35 ℃;
The 5th step: add triethylamine in the reactor in the 4th step, stir 8-10min, under the 800-1000r/min high speed shear, add deionized water emulsification, disperse 25-30min, obtain emulsion;
The 6th step: go on foot even remaining acrylate mixing monomer and the initiator of dripping in the emulsion that obtains the 5th, in 2-3h, dropwise, be warming up to 80-85 ℃ of reaction 1-2h, be cooled to room temperature, obtain the PUA emulsion.
2. the preparation method of a kind of acrylic ester grafted aqueous polyurethane emulsion as claimed in claim 1 is characterized in that described polyether glycol is polyether glycol N220.
3. the preparation method of a kind of acrylic ester grafted aqueous polyurethane emulsion as claimed in claim 1, it is characterized in that, described acrylate mixing monomer is the mixture of soft monomer butyl acrylate and hard monomer methyl methacrylate, and the mass ratio of soft monomer butyl acrylate and hard monomer methyl methacrylate is 1.5-2:1.
4. the preparation method of a kind of acrylic ester grafted aqueous polyurethane emulsion as claimed in claim 1 is characterized in that described initiator is Diisopropyl azodicarboxylate.
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Effective date of registration: 20210120 Address after: Yan Jiang Zhen Shui Yang Cun, Linhai City, Taizhou City, Zhejiang Province Patentee after: DINGLI NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 201108, No. 1038 Jin Du Road, Shanghai, Minhang District Patentee before: SHANGHAI DONGHE ADHESIVE Co.,Ltd. |
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Address after: Yan Jiang Zhen Shui Yang Cun, Linhai City, Taizhou City, Zhejiang Province Patentee after: Dingli New Material Technology Co.,Ltd. Address before: Yan Jiang Zhen Shui Yang Cun, Linhai City, Taizhou City, Zhejiang Province Patentee before: DINGLI NEW MATERIAL TECHNOLOGY CO.,LTD. |